Continuous dyeing of acrylic fiber material



United States Patent 3,436,169 CONTINUOUS DYEING 0F ACRYLIC FIBERMATERIAL Jakob Zurbuchen, Basel-Land, and Jakob Bindler, Riehen,Switzerland, assignors to J. R. Geigy A.G., Basel, Switzerland NoDrawing. Continuation-impart of applications Ser. No.

373,053, and Ser. No. 373,054, June 5, 1964. This application Dec. 2,1965, Ser. No. 511,238 Claims priority, application Switzerland, June11, 1963, 7,282/63, 7,283/63; Dec. 10, 1964, 15,954/64, 15,955/ 64 Int.Cl. D06p 3/76, 3/70 US. Cl. 855 35 Claims This application is acontinuation-impart of our pending patent application Ser. Nos. 373,053and 373,054, both are now abandoned, both filed on June 5, 1964.

This invention relates to the continuous dyeing of acrylic fibermaterials. Continuous dyeing of such fibers has, to our knowledge, notbeen carried out in practice in the past with satisfactory results,namely affording level, fast dyeings on such materials with good coloryields, and free from the undesirable sandwich effect.

It is known that polyacrylonitrile fibers and the like materials ofacrylic fibers are dyed with basic dyestuffs having affinity for theaforesaid fibers batchwise in an exhaustion process (goods-to-liquorratio above 1:5) at pH values within the range of 4.5 to 5.5, with theaid of anion-active or cation-active auxiliary agents which serve asretarders to counteract the tendency of the aforesaid basic dyestuffs todraw too rapidly from the dyebath onto the acrylic fibers, and toprevent lack of uniformity of the dyeings.

Purely non-ionogenic auxiliaries, on the other hand, have been used onlyin known processes for the dyeing of polyamide fibers as retardingagents to attain lighter shades, and for the removal of dyestuff fromthe dyed fibers in the case of insufficient fastness of the dyeings,especially crocking.

The pad dyeing of polyacrylonitrile and the like acrylic fibers,especially in the form of rawstock tows and unrelaxed and steam-relaxedtops which are suitable as starting materials for the manufacture ofyarns, encounters considerable difficulties. In pad-steaming tows ofacrylic fibers, it has been necessary to use as dye assistants inparticular ethylene carbonate and the like cyclic ester, in a bufferedacetic acid medium at the pH range in the vicinity of 5. However, theresulting dye ings often show the so-called sandwich effect, unlevelnessand a relatively fiat, undesirable handle. Blocking out of certaindyestuffs in the conventionally used dyestuff mixtures, with excessiveloss of dye in the rinse and decreased fastness may also result.

It has further been proposed to produce dyeings with basic dye-stuffs onblended fabrics of wool and acrylic fibers by pad-dyeing with a dyeliquor thickened with sodium alginate, and having a substantiallyneutral pH, in the range above 6, and preferably at about 7, as dyeassistants in lieu of ethylene carbonate.

The pad-liquors in this known process have, however, a tendency toflocculate, which leads to streaky dyeings. Moreover, the yield ofdyestuff on the fiber is often unsatisfactory and the textile products,especially acrylic fiber tops dyed in this manner also show a flathandle lacking in volume. A handle 'of satisfactory volume or loftinessis, however, highly desired, for it is known by experience to lead tobetter spinnalbility of the tops and better performance of the towduring cutting into staple fibers, for instance in a turbo-stapler, forthe purpose of making tops or spun yarn.

Moreover, a voluminous handle of textile acrylic fibers is of greatimportance for their further processing in the Patented Apr. 1, 1969manufacture of high bulk yarns therefrom, which latter serve especiallyin the manufacture 'of pullovers and the like textile garments.

The term acrylic fibers as used in this specification and in theappended claims means pure acrylic fibers as defined, for instance, byP. W. Sherwood in Modern Textiles, 44, March 1963, reported in AmericanDyestuff Reporter of June 10, 1963 pages 32 (437) et seq., in contrastto modacrylic fibers defined ibidem. Among the most important acrylicfibers are Orlon, which is nearly pure polyacrylonitrile eopolymerizedwith a small amount of acrylic esters or styrene sulfonic acid, andAcrilan, which contains well in excess of of acrylonitrile together withvinyl pyridines such as methyl vinyl pyridine or other vinyl pyridineslisted, e.g. in Canadian Patent 557,597, and containing acid groupdyesites.

It is, therefore, an object of the present invention to provide acontinuous dyeing process, preferably by pad steaming, for acrylic fibermaterials such as rawstock, tows and fabrics, and, especially, however,acrylic fiber tow or tops destined for the manufacture of high bulkyarns, whereby dyed materials are produced which are distinguished bydeeper shades, freedom from sandwich effects and uniformity of shade,especially, also, when dyeing is carried out with dyestuff mixtures, andwhich, especially in the case of tops and tows, are distinguished by aloftier, more voluminous handle.

This and other objects which will become apparent as the description ofthe invention proceeds, are attained by a process for the continuousdyeing of polymeric and copolymeric acrylonitrile fibrous material whichcomprises, according to a first aspect of the invention, using adyestuff preparation consisting of optionally thickened aqueous, acidsolution of basic dyestuffs, soluble salts of saturated carboxylic acidshaving 8 to 14 carbon atoms and surface active hydrophilic towater-soluble polyglycol ethers having lipophilic radicals, andsufficient amount of a water-soluble strong, preferably organic acid,especially an acid as defined in detail hereinafter, to make the pH ofthe preparation 2 to, at most, 4.3 and preferably 2.5 to 4.0 and whichpreparation can contain other auxiliaries, particularly amides ofsaturated, aliphatic monocarboxylic acids having 8 to 14 carbon atomswith primary or secondary alkanol-amines. The goods are impregnated withthese preparations at temperatures lying below the drawing temperatureof the dyestuffs and then subjected to moist heat treatment by the usualmethods.

The acidity of the impregnating liquor is brought about by addingthereto organic acids as defined above, particularly odorless loweralkanoic acids such as acetic acid or formic acid, but also suchindustrially available acid as tartaric acid. These are added in amountsof 30 to 300 g. and, preferably, 40 to 60 g. per liter of impregnatingliquor in order to ensure that the pH of the liquor is below 4.5,preferably between 2.5 to 4.0. Strong acids being suitable in theprocesses according to the invention are those, the pK value of whichfor at least the first hydrogen is below 5.

This high acidity of the impregnation liquors according to the inventionor dyestuff-dye carrier pastes used for their preparation is a veryimportant feature of the invention.

Hitherto, when no acid at all or considerably smaller amounts of acidwere used, e.g. in concentrations of 2 to 6 g. per liter, low coloryields were obtained, the dyeings showed pronounced sandwich effects, orthe dyestuffs were partially destroyed, leading to undesirable shifts inshade, especially in the dyeings of some types of acrylic fibermaterials, particularly from among those having carboxyl groups asdyesites, which tend to split off alkali when treated with boiling dyeliquors.

The impregnating liquors according to the first aspect of the inventioncontain as salts of suitable saturated carboxylic acids having 8 to 14carbon atoms, especially the salts which are more specifically describedhereinafter under the first preferred mode of carrying out this aspectof the invention in practice.

As surface active, hydrophilic to Water-soluble polyglycol etherscontaining lipophilic radicals according to the invention, the dyestuffpreparations according to the invention contain polyglycol ethers,particularly ethylene oxide condensation products of alkyl phenolscontaining one or more alkyl substituents which together contain atleast 8 carbon atoms; of primary or secondary, monoor poly-basicaliphatic and cycloaliphatic amines containing at least one higher alkylor alkenyl radical having at least 8 carbon atoms, or of alkanaolaminescontaining such lipophilic alkyl and aralkyl radicals; and also ethyleneoxide condensation products of alkanolamides, aminoalkylamides andaminoalkyl esters of higher, aliphatic carboxylic acids and higheralkylated alkylaryloxy carboxylic acids, into all of which ethyleneoxide condensation products can be built individual substituted epoxidessuch as styrene oxide and/ or propylene oxide.

The amount of auxiliaries mixture per liter of dye liquor is, e.g. 2 to100 g. and, preferably, to 40 g.

The weight ratio of the soluble fatty acid salt to the polyglycol ethersaccording to the first aspect of the invention should be smaller than3:1 and preferably at about 2:1 to 1:2. When mixtures containing thesalts mentioned, polyglycol ethers and amides are used, then the ratioby weight of the said salts to the polyglycol ether/ amide mixture issmaller than 3 :1 and preferably in the range of 2:1 to 1:8.

As basic dyestuffs, dyestuif preparations according to the inventioncontain conventional salts and metal halide, e.g. zinc chloride, doublesalts of known cationic dyestuffs, in particular of methine orazamethine dyestuffs which contain the indolinium, pyrazolium,imidazolium, triazolium, tetrazolium, oxdiazolium, oxazolium,thiazoliurn, pyridinium, pyrimidinium, pyrazinium ring. The heterocyclesmentioned can optionally be substituted and/ or condensed with aromaticrings. Also, cationic dyestuffs of the diphenylmethane,triphenylmethane, oxazine and triazine series can be used and, finally,also color salts of the arylazo and anthraquinone series having anexternal onium group.

Thickeners suitable for use in an acid bath are, e.g. the soluble typesof gum usual in the textile industry, e.g. so-called crystal gum orthickeners having a cellulose basis such as locust bean flour,tragacanth, British gum or cellulose derivatives such as methylcellulose or soluble salts of carboxymethyl cellulose. Locust bean flourthickeners and galactomannan thickeners are preferred.

As other auxiliaries usual in the dyeing industry, the impregnatingliquor can contain, e.g. organic solvents, in particular ethylene glycolmonoethyl ether or thiodiethylene glycol and also ethylene carbonate.

Polymeric or copolymeric acrylonitrile fiber materials suitable fordyeing by the process according to the invention are acrylic fibers,i.e. fibers of which 8010'0% consists of polymeric acrylonitrile, andwhich contain acid dyesites, more particularly sulfonic acid and/orcarboxylic acid dyesites.

The acrylic fiber can be dyed according to the invention in any formdesired, e.g. in the form of rawstoc-k material, yarn or fabrics,particularly however in the form of tow or slubbing.

The fibrous material is impregnated, for example, by printing, coatingor spraying, preferably however, by pad dyeing in the foulard.

The impregnating liquor according to the invention is advantageouslyproduced by pasting the basic dyestuff with the amount of acid used,particularly with the required amount of acid, preferably a 6080% aceticacid being used, adding hot water to the paste and then adding the saltsand polyglycol ethers as well as, optionally, other auxiliaries usuallyemployed in the dyeing industry.

The polyacrylonitrile fibers are advantageously impregnated at 30 to C.and then squeezed out to leave on the fibers the desired content ofimpregnating liquor of about m 130% calculated on the dry weight of thefiber material.

The impregnated fibers are then steamed by the usual methods,advantageously with neutral saturated steam, or, preferably, slightlyoverheated steam.

The dyed and steamed goods are subsequently rinsed, advantageously withcold or warm water which can contain the additive usual in the dyeingindustry, e.g. formic acid or acetic acid or also substances renderingthe goods antistatic or fabric softeners.

By the process according to the invention, particularly in thecontinuous dyeing of polymeric and copolymeric acrylonitrile fibers,very deep shades free from sandwich effects are obtained which aredistinguished by the evenness of the dyeing. In particular, in thepreferred continuous dyeing with a mixture of difierent basic dyestufls,there is no selective dyeing of the fibers.

Polyglycol ethers containing basic nitrogen are particularly valuable inthe process according to the invention, for example, polyglycol ethersof aliphatic, particularly higher alkylated or acylated diandpolyamines, whereby one long or several shorter polyglycol ether chainscan be bound by way of the nitrogen, such as ethylene oxide condensationproducts of higher monoalkylor alkenylethylene-diamine,-diethylenetriamine, -triethylenetetramine or of lauroyl-, myristoyl-,oleoyl-, palmitoyl-, stearylaminoethylamine, -ethylenediamine,-diethylenetriamine. Depending on the type and composition of thelipophilic component of these compounds, the number of alkyleneoxy,especially ethyleneoxy groups in these polyglycol ethers is, in all, atleast 4, preferably more than 8 to about 100 ethyleneoxy radicals. Theycan be arranged in one single or in different chains and, to strengthenthe lipophilic character, also single ethyleneoxy groups can bealkyl-substituted (particularly methyl-substituted) orphenyl-substituted.

The number of alkyleneoxy groups in these polyglycol ethers shouldensure hydrophilic properties and should be so great that the compoundsare, at least, easily dispersible in water and, preferably are solubletherein. The use of mixtures of these substances with low to highcontents of ethyleneoxy groups is often advantageous and leads to betterdispersions. Examples of polyglycol ethers containing lipophilic groupswhich are usuable according to the invention are:stearyl-diethylenetriamine polyglycol ethers with 17 ethyleneoxy groups,addition product of 2 mols of styrene oxide and 50-60 mols of ethyleneoxide to 1 mol of stearyl-diethylenetriamine, nonylphenol polyglycolethers with 5 ethyleneoxy groups, coconut oil fatty aciddi-fl-hydroxyethylamide polyglycol ethers with 15-17 ethyleneoxy groups,octylphenoxyacetic acid polyglycol ethers with 3-5 ethyleneoxy groups,addition product of 2 mols of 1,2-propylene oxide and 50-60 mols ofethylene oxide to 1 mol of stearyl-diethylenetriamine, oleylaminepolyglycol ethers with 7 ethyleneoxy groups, stearoyldiethylenetriaminepolyglycol ethers with 17 ethyleneoxy groups, octylphenol polyglycolethers with 4 ethyleneoxy groups and higher fatty acid,acid-B-amino-lower alkyl ester polyglycol ethers with 3 ethyleneoxygroups.

It is particularly advantageous if the impregnating liquor also containsamides in addition to the fatty acid salts and the polyglycol ethers.

The amides usable according to the invention are derived from the higherfatty acids mentioned above in connection with the salts and frommonohydroxyalkylamines, e.g. from fi-hydroxyethylamine,'y-hydroxypropylamine or [3, -dihydroxypropylamine, frombis-(w-hydroxyalkyl)-amines such as bis-(fi-hydroxyethyD-amine orbis-('y-hydroxypropyl -amine or bis-(ot-methyl-fi-hydroxyethyl)-amine orN-alkyl-N(w-hydroxyalkyl)-amines such as N-methylor N-ethyl-N-(B-hydroxyethyD-amine or N-methylor N-ethyl-(y-hydroxypropyl)-amine.

The bis-(w-hydroxyalkyl)-amides are preferred, particularly those thehydroxyalkyl radicals of which contain two or three carbon atoms such asbis-(fl-hydroxyethyU- amides or bis-('y-hydroxypropyD-amides of coconutoil fatty acids.

A preferred mode of carrying out the first aspect of the invention inpractice comprises especially in the dyeing of acrylic slubbings, butalso of the other acrylic fiber materials mentioned hereinbefore:

Mixing a cationic (basic) dyestuff with a water-soluble strong organicacid, preferably, acetic acid of a content of from about 60% of CH COOH,in the case of aqueous dilute acetic acid, up to pure glacial aceticacid and diluting the dyestuff-acid mixture with hot water to aconcentration of from to 350 grams (g.), and preferably from to 60 g. ofglacial acetic acid (CH COOH) per 1000 g. of final impregnation liquor,the amount of dyestuff corresponding to saturation of the final liquortherewith at a temperature of 40 to 60 C. in those cases where deepshades are desired;

Adding to the resulting mixture, as a dyestuif migration controlling dyeassistant one of the following compositions:

(I) A dye assistant composition consisting of:

(a) a water-soluble salt of a saturated aliphatic monocarboxylic acid offrom 8 to 14 carbon atoms, the cation of which is selected from thegroup consisting of alkali metal ion, ammonium ion, loweralkyl-substituted ammonium ion, hydroxy-lower alkyl-substituted ammoniumion, lower alkoxy-lower alkyl-substituted ammonium ion and hydroxy-loweralkyl-substituted ethylene-diammonium ion; and

(5) A polyglycol ether obtained by condensing:

(1) A compound selected from the class consisting of (i) a fatty,preferably saturated alcohol of from 8 to 20 carbon atoms,

(ii) a fatty, preferably saturated acid of from 8 to 20 carbon atoms,

(iii) an alkyl-substituted phenol wherein alkyl has a total of at least8, and preferably from 8 to 12 carbon atoms,

(iv) the reaction product of a higher fatty, preferably wholly saturatedalcohol of from 8 to 20 carbon atoms and ammonia, or an aliphatic/ aminehaving from 2 to 4 basic nitrogen groups separated from each other byfrom 2 to 3 carbon atoms, in a molar ratio of about 1:1,

(v) the amide of a preferably wholly saturated fatty acid of from 8 to20 carbon atoms amidified with a mono, dior tri-hydroxy-loweralkylsubstituted amine, with, per mol of (1) (2) from 2 to 100 mol, andpreferably from 8 to 60 mol of ethylene oxide, from 0 to 2 mol ofpropylene oxide and from 0 to 2 mol of styrene oxide; or

( 8') a polyglycol ether obtained by condensing:

(vi) an amino-lower alkyl ester of a preferably wholly saturated fattyacid of 8 to 14 carbon atoms, with, per mol thereof,

(2') from 2 to 10 mols of ethylene oxide: or

(I') a dye assistant composition consisting of:

('y) an amide of (a) a preferably wholly saturated aliphatic carboxyiicacid of from 8 to 20, and preferably 8 to 14 carbon atoms, or

(b) an alkyl phenoxy-substituted lower alkanoic acid wherein the alkylsubstituent has from 8 to 12 carbon atoms,

amidified with a member selected from the group consisting of mono-,diand tri-hydroxy-lower alkyl amines and the lower alkyl ethers thereof;and

(,8) a polyglycol ether which is the condensation product of a memberselected from the group consisting of a saturated fatty alcohol of from8 to 14 carbon atoms and a saturated aliphatic monocarboxylic acid offrom 8 to 14 carbon atoms, with from 5 to 30 mols of ethylene oxide permol of said member; which dye assistant composition is added in anamount of at least about 10 grams and preferably from 10 to grams perliter of said impregnation liquor,

as well as an acid-medium-compatible thickener in sufficient amount toimpart to the resulting impregnation liquor a viscosity of at leastabout 30 centipoises;

(A) Impregnating acrylic fiber material with the aforesaid impregnationliquor,

(B) Removing excess liquor from the impregnated acrylic fiber materialto leave on every 100 parts by weight of the said material from about 80to parts by weight of liquor;

(C) Steaming the resulting impregnated material with saturated steam forabout 15 to 30 minutes, and

(D) Rinsing the steamed material with water and drying the same.

Optimal all-round results are obtained when, in lieu of the binary dyeassistant compositions defined above, there are used ternarycompositions (1") which consist of (a) A water soluble salt of asaturated aliphatic monocarboxylic fatty acid having 8 to 14 carbonatoms with a monoto divalent cation selected from the group consistingof alkali metal ion, ammonium ion, lower alkylsubstituted ammonium ion,hydroxyl-loWer-substituted ammonium ion,

(5) A polyglycolether which is obtained (1) as condensation product froma member selected from the group consisting of a saturated fatty alcoholof from 8 to 14 carbon atoms and a saturated fatty acid of from 8 to 14carbon atoms, and per mol of said member, 4 to 12 equivalents ofethylene oxide, or

(ii) or as condensation product from the reaction product of a higherfatty alcohol of from 8 to 20 carbon atoms and an aliphatic polyaminehaving at least 2 and not more than 4 basic nitrogen groups separatedfrom each other by from 2 to 3 carbon atoms, in a molar ratio of about1:1, with, per mol of said reaction product, from 10 to 60 mol ofethylene oxide, 0 to 2 mol of propylene oxide and 0 to 2 mol of styreneoxide,

and

(7) An amide of a saturated aliphatic mono-carboxylic acid having from 8to 14 carbon atoms amidified by a member selected from the groupconsisting of monoand di-hydroxy-lower alkyl-amines and lower alkylethers thereof, the weight ratio of (a) to the sum of (,8) and (7) beingsmaller than 3:1, and preferably in the range of 2:1

Highest color yields are obtained with those of the ternary dyeassistant compositions defined above in which component ([3) is acondensation product as defined under (i), supra.

The ratio of fivy is not critical.

In lieu of the dye assistants enumerated above, it is also possible touse a polyglycol ether defined as component (B) or (fl) of dye assistantcomposition (1), su ra, alone, but this leads to undesirable foamformation during padding and also imparts to the dyed tow a. less lofty,drier handle and can affect detrimentally the running properties of thedyed material, especially in the Turbo stapler.

That the use of the substantially non-ionogenic or mixednon-ionogenic/anionic dye assistants in the process according to theinvention prevents the formation of the undesirable sandwich eifect andfavorably controls the migration of the dyestuif during steaming isespecially unexpected, for anionic dye assistants alone, as they havebeen used in the dyeing of polyacrylonitrile fibers in the batchprocess, and especially water-soluble salts of saturated fatty acids of8 to 14 carbon atoms of the type mentioned above, when used as theexclusive dye assistant in the process according to the invention, leadto uneven dyeings in particular in the case of the preferred compounddyeing, i.e. dyeing with dyestutf mixtures, in which case thelast-mentioned anionic agents lead to dyeing in ununiform shades of thevarious dyestuffs in the mixed dyes.

Furthermore, it is particularly suprising that better dyestuff yieldswith equally good or even better fastness properties are achieved in theprocess according to the invention with the above-listed dye assistantson acrylic fiber materials in a stronger acid medium than had hithertobeen recommended; for it would have been expected that a stronger acidmedium would decrease the dissociation of the basic dyestuffs,especially the more conventionally preferred ones yielding, in aqueoussolution, a pH in the range of 3 to 5, and would also decrease thedissociation of the dyestuff-afiinic groupings in the acrylic fibermolecules, and would thus increase the tendency of the dyestuff toremain in the dye liquor and decreas the receptivity of the acrylicfibers for the dyestuff.

However, contrary to that expectation, when using the above-listeddye-assistants in a pad liquor of the above-defined pH range, of about 2to 4, and preferably about 2.5 to 3.5 the receptivity of the acrylicfibers, especially of acrylic tows or tops, is markedly improved, ascompared with the various known pad-steaming methods at pH rangesbetween 4.5 and 7 and higher, mentioned above.

A further unexpected advantage of the process according to the inventionresides in the fact that the resulting dyed tows or tops possess asubstantially loftier, more voluminous, fuller handle than thoseobtained under otherwise identical conditions with a pad liquor of a pHabove 4.5 which contains the hitherto used dye assistants.

As salts of suitable saturated aliphatic monoearboxylic acids, the dyeassistants used in the impregnating liquors according to the firstaspect of the invention contain, for example, alkali metal salts such aslithium, sodium or potassium salts, ammonium or N-substituted ammoniumsalts of caprylic, pelargonic capric, lauric or myristic acid or themixtures of acids comprised by the generic term coconut oil fatty acids,or of decyloxyacetic acid, lauryloxy acetic acid, decylthioacetic acidor lauryl thioacetic acid. N-substituted ammonium salts contain assubstituent or substituents of the amino nitrogen atom, in particular,lower alkyl such as the methyl or ethyl group, hydroxy-lower alkylgroups such as the fi-hydroxyethyl or 'y-hydroxypropyl group, or loweralkoxy-lower alkyl such as the B-methoxyethyl or ,B-ethoxyethyl or'y-methoxyp-ropyl or 'y-ethoxypropyl group. Two of these N-substituentstogether with the amino nitrogen atom can also form a ring, inparticular, the piperidine or morpholine ring.

The alkali metal, the lower alkyl ammonium or hydroxy-lower alkylammonium salts, chiefly the monoand bis-(fl-hydroxyethyl)-ammonium ormonoand bis-(yhydroxypropyl)-ammonium, the N-methyl-N-(fi-hydroxyethyl)-ammonium, N-methyl-N,N-bisfi-hydroxyethyl ammonium orN-methyl-N-(l3,'y-dihydroxypropyl)-amm'onium salts of coconut oil fattyacids have proved to give particularly satisfactory results ascomponents in the dye assistant mixture defined under (I), supra.

The acid reaction of the impregnating liquor is brought about by theaddition of adequate amounts of fatty acid; most advantageously theimpregnation liquor contains the above-given amounts of acetic acid. ThepH of the impregnation liquor is then between 2 and 4.5, and preferablyadjusted to 2.5 to 3.5.

Polyglycol ethers particularly suitable for use as dye assistants in theprocess according to the invention, either alone or, preferably, inmixture with other components as defined above under (I), (I') and (1"),are the reaction products of 4 to 30, preferably 8 to equivalents ofethylene oxide, with 1 equivalent of octyl, decyl, dodecyl or tetradecylalcohol, or with the fatty alcohol mixture comprised by the term coconutoil fatty alcohol or with 1 equivalent of a fatty acid, e.g. one of thefatty acids mentioned above, in particular coconut oil fatty acid.

Amides which are usable in the dye assistants according to the inventionare obtained, for example, from the higher fatty acids discussed aboveby amidification with monohydroxy-lower alkylamines, e.g.fi-hydroxyethylamine, 'y-hydroxypropylamine or B -dihydroxypropylamine,or bis-(hydroxy-lower alkyl)-amines such as bis- (fl-hydroxyethyU-amineor bis-(y-hydroxypropyl)-amine or bis- (a-methyl-fl-hydroxyethyl)-amine,or N-lower alkyl-N-(hydroxy-lower alkyl)-amines such as N-methylorN-ethyl-N-(B-hydroxyethylamine) or N-methylor N- ethyl-N-('y-hydroxypropyl) -amine.

The bis-(hydroxy-lower alkyl)-amides are preferred, in particular thosethe hydroxyalkyl radicals of which contain two or three carbon atoms,especially the bis- (fl-hy'droxyethyl) amides orbis-(y-hydroxypropyhamides o-f conconut oil fatty acids.

The basic dyestuffs usable according to the invention are preferablysulfonic acid group-free dyestuffs of the thiazine, oxazine,diphenylmethane, triphenylmethane, rhodamine, azoor anthraquinone seriesand, preferably, metliines and azamethines which, in particular, containonium groups, ammonium groups in particular being regarded as a type ofonium group.

Acid medium-compatible thickeners usable in the process according to theinvention, are in particular of gum conventional in the textileindustry, e.g. so-called crystal gum or thickeners having a cellulosebasis such as carob bean flour, tragacanth, British gum, cellulosederivatives such as methyl cellulose or water-soluble salts ofcarboxymethyl cellulose, or galactomannan. Carob flour thickeners arepreferred.

The acrylic fiber materials are impregnated, for example, by printing,coating or spraying, preferably however, by the foulard process.

As has been described above, the impregnating liquor according to theinvention is produced advantageously by adding to acetic acid, the basicdyestuif, water, the dye assistant as defined above under (I), (1) and(1") and thickener.

The fibers can be dyed in any form desired, for example in the form ofloose fibers, tops, yarn or fabrics, but especially as tops or tow, orrawstock.

Advantageously, the polyacrylonitrile fibers are impregnated with theimpregnation liquor at 3050 C. preferably at 4045 C. and thensqueezedout to the desired content of impregnating liquor of about to ofthe weight of the fiber.

The impregnated fiber material is steamed by conventional methods,advantageously with neutral saturated steam.

The padded and steamed goods are advantageously rinsed, preferably withcold or warm water which can contain the additives usual in dyeing, e.g.formic acid or acetic acid and/or substances rendering the goodsantistatic, or softeners.

Compared with similar known processes and even compared with the otheraspects of this invention, the preferred process mode according to thisaspect of the invention for the dyeing of polymeric and copolymericacrylonitrile fibers has the following advantages; apart from thosementioned hereinbefore:

(l) The impregnating liquor is homogeneous and substantially insensitiveto salts and acids, it is therefore stable in the continuous dyeingprocess;

(2) Even when producing very deep shades, excellent uniformity of thedyeing is attained;

(3) The impregnating liquors are easily produced and can be stored,practically, for an unlimited time;

(4) No undesirable sticking of the liquors to the squeeze rollersoccurs;

(5) Color yield and levelness of dyeings, and often also the fixingspeed during steaming, are optimal, especially with the above-mentionedamide-component containing ternary compositions.

In lieu of acetic acid, other acids of similar strength can also be usedin the process according to the invention, e.g. formic acid or tartaricacid, and also sulfuric acid, provided that the pH of the impregnationliquor ready for use is within the above-stated critical range.

A second aspect of the invention concerns a process for the continuousdyeing, of acrylic fiber materials which is characterized in that thematerial is impregnated with a preferably thickened, aqueous acidsolution of basic dyestuff, with solution contains in amounts of 0.2 to10% and preferably 0.5 to 5% by weight of the whole liquor, of a dyeassistant which consists essentially of a polyglycol ether obtained bycondensing (I) a compound selected from the class consisting of (a) afatty, preferably saturated alcohol of from 8 to 20 carbon atoms, or

(b) a fatty, preferably saturated acid of from 8 to 20 carbon atoms,

() an alkyl-substituted phenol wherein alkyl has a total of at least 8,and preferably from 8 to 12 carbon atoms.

(d) the reaction product of a higher fatty alcohol of from 8 to 20carbon atoms and an aliphatic polyamine having from 1 to 4, andpreferably from 2 to 4 basic nitrogen groups separated from each otherby from 2 to 3 carbon atoms, in a molar ratio of about 1:1, or

(e) the amino-lower alkyl ester of a preferably wholly saturated fattyacid of 8 to 14 carbon atoms,

(f) the amide of a preferably wholly saturated fatty acid of from 8 to20 carbon atoms amidified with a mono-, dior tri-hydroxy-loweralkyl-substituted amine,

mixtures of two or more of said members (a) to (f) with, per mol of (I),

(II) From 4 to 100 mol, and preferably from 8 to 60 mol of ethyleneoxide, from 0 to 2 mol of propylene oxide and from 0 to 2 mol of styreneoxide, each of (a), (b) and (c) being preferably condensed with to 12,and each of (d), (e) and (f) with 4 to 20 mols of ethylene oxide alone,per mol of compound (I); or mixtures of such condensation products, andthe pH of the solution is adjusted to a value below 4.5 and preferablyto a value in the range of 2.5 to 4.0, by adding adequate amount ofwater soluble, strong organic carboxylic acid, the impregnation beingperformed at temperatures below the drawing temperature of thedyestuffs, and the treated goods are then subjected to a moist heattreatment by conventional methods.

It is particularly surprising that, for instance, polyglycol ethers suchas are obtained by condensation of compounds of type (f), supra, withethylene oxide, which polyglycol ethers are well known as retardingagents in the exhaustion dyeing of polyamide such as wool, act as dyeingassistant in the pad-dyeing of acrylic fiber materials which actuallyhelp to bring about high color yields in a shorter time and completefixing of such high yield by short-time steaming, especially withslightly superheated steam.

The conditions of treatment set forth under the first aspect of theinvention apply equally to this second aspect.

Very deep shades free from sandwich effects are obtained by thecontinuous dyeing process according to the invention, on polymeric andcopolymeric acrylonitrile fibers. The dyeings are distinguished byexcellent evenness. In particular, in the preferred continuous dyeingwith a mixture of different basic dyestuffs, no spots occur on thefibers which are selectively dyed.

The polymeric and copolymeric acrylonitrile fibers which can be dyedaccording to this second aspect of the invention are acid-modifiedpolymer fibers and contain at least 80% acrylonitrile, as defined above;they should be fabrics, preferably in the form of woven or piece goodssuch as plush.

Fabrics are preferred because liquors according to this aspect of theinvention have a tendency to adhere more to the squeeze rollers of thepad mangle and to cause more foam than do the liquors falling under thefirst aspect of this invention. These drawbacks are more serious whenpad-dyeing slubbings, tow or rawstock, but not so much when dyeingfabrics.

As hydrophili-c to water soluble, surface active polyglycol ethers, thedyestuff preparation contains the polyglycol ethers describedhereinbefore, and more particularly ethyleneoxy condensation products,into which a few substituted epoxides such as styrene oxide and.propylene oxide can be built, of fatty alcohols, i.e. alkanols andalkenols having 8 to 20 carbon atoms; of fatty acids having 8 to 20carbon atoms; of alkyl phenols having one or more alkyl substituentswhich together contain at least 8 carbon atoms; of primary or secondarymonoor polybasic aliphatic and cycloaliphtaic amines containing at leastone higher alkyl or alkenyl radical having at least 8 carbon atoms, orof such alkanolamines having lipophilic alkyl and aralkyl radicals; alsoof alkanolamides, aminoalkylamides and aminoalkyl esters of higheraliphatic carboxylic acids and higher alkylated alkylaryloxv carboxylicacids.

Basic nitrogen-containing polyglycol ethers of aliphatic. particularlyhigher alkylated or acylated diand polyamines are particularly valuablein the process according to this aspect of the invention, such as thepolyglycol ethers of N-monoalkylor N-monoalkenylmonoor -dior -tri or-tetralower alkylene-di-, or -trior -tetraor -pentaamines having atleast 16 carbon atoms in the alkyl or alkenyl radical and at least 15and preferably more than 25 to about ethyleneoxy radicals, of which afew can be C-methylated and/or C-phenyl substituted. Particularlyfavourable compounds of this type are addition products of 15 to 20 molsof ethylene oxide to an N- monoalkyl diethylenetriamine the alkylradical of which contains at least 16 carbon atoms, e.g. a stearyldiethylenetriamine, or addition products of l to 3 mols of styrene oxideor propylene oxide and at least 50 mols of ethylene oxide to anN-monoalkyl diethylenetriamine the alkyl radical of which has 16 to 18carbon atoms.

Another valuable group of polyglycol ethers are de fined are those ofalkanols, alkenols and alkyl phenols which contain hydrophobichydrocarbon radicals of, in all, at least 8 carbon atoms and at least 5ethyleneoxy radicals. Particularly suitable compounds of this type areaddition products of 4 to 20 mols of ethylene oxide to one alkanolhaving 8 to 18 carbon atoms such as hexadecanol, or to a .mixture offatty alcohols known by the general term coconut oil fatty alcohol or analkyl phenol which contains alkyl radicals having, in all, at least 8carbon atoms e.g. octylphenol or nonyl phenol or ditert. butyl phenol.

Examples of other suitable polyglycol ethers as defined are:acylaminoalkyl monoor poly-amines which contain hydrophobic hydrocarbonradicals of at least 8 carbon atoms and at least 10 ethyleneoxyradicals, preferably more than 25, of which a few can be C-alkyl orC-aryl substituted. Examples of such compounds are addition products ofat least 10 mols of ethylene oxide to lauroyl, myristol, oleoyl,palmitoyl or stearoyl amino-ethylamine, -ethylenediamine or-diethylenetriamine.

In a third aspect, this invention relates to yet another process for thecontinuous dyeing (pad dyeing or printing) of polymeric and copolymericacrylonitrile fiber materials and especially of acrylic tow, animpregnating liquor suitable for this process as well as, as industrialproducts, the fibers dyed With the aid of this liquor.

It is known that natural and synthetic polyamide fiber-s, for examplewool or nylon, can be dyed by a continuous process if an impregnatingliquor is used which, in addition to acid wool dyestuffs, contains ascarrier, watersoluble condensation products of 1 equivalent of fattyacids having 8 to 14 carbon atoms or mixtures of such fatty acids and 1to 3 equivalents of mono, diand/or tri-alkanolamine. Such condensationproducts have been described in US. Patent No. 2,089,212. Impregnatingliquors containing such carriers require conventionally alkaline toneutral pH-values. It was not to be expected that the aforesaid carrierscould be used as dye assistants for the dyeing for polymeric andcopolymeric acrylonitrile fiber material with basic dyestuffs from anacid medium.

Particularly, it could not have been expected that an improvement of theaffinity of basic dyestuffs to acrylonitrile fibers could be attained byworking with such auxiliaries in a stronger acid medium. Rather, it wasto be expected that in a stronger acid medium there would be lessdissociation of the dyestuff so that it would tend to remain in the dyeliquor and, in addition the dissociation of the substituent groupshaving affinity to the dyestuff and hence constituting dyesite in thefiber molecules would be retarded so that, again, the amount of dyestuffwhich the fibers could take up would be reduced. We have found, however,that just the opposite happens and that, when dyeing is performed inrelatively strong acid medium, i.e. at pH values of about 3.5 to 4 andbelow, basic dyestuffs are considerably better taken up by acrylonitriletow than when dyeing is performed in a weakly acid medium, i.e. at pHvalues of about 5 to 7 or higher.

Another surprising advantage of the process according to the inventionis that the products attained, in particular polyacrylonitrile tow, aredistinguished by a considerably more voluminous, full handle, whereasproducts produced by known processes have a fiat handle ofunsatisfactory volume.

Experience has shown that when tow has a voluminous handle, it can bebetter spun and has better spinning properties on stapling (cutting) thetow, for example, in a turbostapler. In addition, a voluminous handle ofthe products produced according to the invention is decisive for theirfurther use for the production of high bulk yarns used, mainly, for themanufacture of pullovers and similar textile articles. The spotty, shinyappearance of the tow produced by known processes is undesirable for themanufacture of such articles.

Contrary to expectation, it has now been found that polymeric andcopolymeric acrylonitrile can be dyed, particularly continuously,surprisingly well and in deep shades by impregnating this material witha thickened aqueous acid impregnating liquor, the acid reaction of whichimpregnating liquor is due mainly to the presence of low fatty acids, inparticular of acetic acid, which is added in amounts of 30 to 300 gramsg.) and preferably of 40 to 60 g. of CH COOH (100%) per liter of theimpregnation liquor, to attain a pH-value of the liquor below 4.5,preferably between 2.5 and 4.0, and which impregnating liquor containsbasic dyestuff, acid-mediumcompatible thickener, and, as dyeing controlagent, watersoluble condensation product of 1 equivalent of fatty acidshaving 8 to 14 carbon atoms or of mixtures of such fatty acids,condensed with l to 3 equivalents of diand/or tri-alkanolamine, as wellas, optionally, other auxiliaries conventional in pad dyeing, theimpregnation being performed at a temperature below the drawingtemperature of these dyestuffs, and steaming the treated goods byconventional methods.

The total amount of the condensation product per liter of theimpregnation liquor ranges from 15 to 100 g. and, preferably, from to 40g.

The fatty acid diand/or tri-alkanolamine condensation products used inthe impregnating liquor according to this aspect of the invention can beproduced by the process described in the US. Patent No. 2,089,212already mentioned, namely, by heating 1 equivalent of fatty acids with 1to 3 equivalents of diand/or trilower alkanolamines, particularly di ortri-ethanolamine While splitting off more than 1 mol of water. Thecommercial mixtures known as coconut oil fatty acids are chiefly used asfatty acids for this purpose. They consist mainly of lauric acid and, inaddition, contain varying amounts of the fatty acids having 8, 10 and 14carbon atoms. Although diethanolamine in a molar ratio of 2 mols ispreferred, it can be wholly or partially replaced by other loweralkanolamines, eg by triethanolamine, di-2- propanol-amine ordi-3-propanolamine. In particular, on using tri-alkanolamines and fattyacids having 8 to 12 carbon atoms, a satisfactory dispersability of thecondensation product in the dye liquor is achieved even when using inthe condensation of the said product a molecular ratio of 1:1 andsplitting off only one mol of water. Generally, however, it is ofadvantage if a multiple of the stoichiometrical amount, preferably twicethe amount, of alkanolamine is used in the condensation reaction. It isalso favorable when at least one mol of the alkanolamine used containshydrogen bound to the nitrogen atom so that acid amide formation ispossible.

The basic dyestuffs used according to the invention are advantageouslyof the following classes of dyestuffs: thiazines, oxazines, diphenylmethanes, triphenyl methanes, rhodamines, azo or anthraquinone dyestuffswhich, in particular, contain onium groups, and, preferably, methinesand azamethines; ammonium groups in particular being regarded as oniumgroups.

Examples of thicknes which are compatible with an acid medium are thesoluble types of gum usual in the textile industry, e.g. so-calledcrystal gum or thickeners based on cellulose such as locust bean flour,tragacanth, British gum, polysacharides or cellulose derivatives such asmethyl cellulose or soluble salts of carboxymethyl cellulose. Locustbean flour thickneners are preferred. Galactomannan may also be used.

The padding liquor can contain as other auxiliaries usual in the textileindustry, for example organic solvents such as ethyleneglycolmonoethylether or thiodiethylene glycol, as well as ethylene cycliccarbonate.

As polymeric and copolymeric acrylonitrile fibers, particularly thoseare meant the greater portion of which, preferably to practicallyconsists of this material which possess an adequate number of dyesites.

The acrylic fibers are impregnated, for example, by printing, coating orspraying, preferably, however, by padding.

The impregnating liquor according to the invention is advantageouslyproduced by pasting the basic dyestuff with the above-defined amount ofacetic acid, preferably 60 to 80%-acetic acid, adding to the mixture hotwater and an aqueous solution of the condensation products as defined,and, optionally, other auxiliaries usual in dyeing and thickener.

The acrylic fibers can be dyed according to the invention in the formdesired, for example, in the form of flocks, yarn and fabrics, andespecially in the form of tow, top or rawstock.

The polyacrylonitrile fibers are advantageously impregnated at 30-40" C.and then freed from excess of impregnating liquor to leave on the fibersonly a content of impregnating liquor of about 60 to calculated on thedry weight of the fibers.

The impregnated fibers are steamed by conventional methods,advantageously with neutral saturated steam, without intermediatedrying.

The dyed and steamed goods are advantageously rinsed, preferably withcold or warm water which can contain the additives usual in dyeing, e.g.formic acid or acetic acid or also substances which make the goodsantistatic, or softeners.

By following the process according to the invention, dyeings onpolymeric and copolymeric acrylonitrile fibers of very deep shades areobtained, which are distinguished by their excellent uniformity.

Particularly when using a mixture of different basic dyestuffs, as ispreferred in continuous dyeing, the undesirable selective dyeing of thedifferent dyestufi components of the mixture is avoided and fibermaterial dyed in perfectly level deep shades is obtained.

When compared with the impregnation liquors of the first aspect of theinvention, and especially the preferred mode of carrying the latter outin practice, the liquors of this third aspect are somewhat less stableat higher temperatures (above 50) and may show a tendency to formseparate layers. Also they tend to greater formation of foam.

The follOWing non-limitative examples serve to illustrate the severalaspects of the invention. The temperatures are given therein in degreescentigrade. Where not otherwise expressly stated, parts and percentagesare given by weight. The relationship of parts by weight to parts byvolume is as that of grams (g.) to milliliters (ml.).

Example 1 19.2 g. of the red dyestuff of the formula I ICH3 bill /C2H56.2 g. of the yellow dyestuff of the formula are pasted with 80 ml. ofcold 60% acetic acid, and 200 ml. of hot water are added thereto.

40 g. of a dye assistant composition consisting of 35 parts ofN-methyl-N,N-bis-(fi-hydroxyethyl)-ammonium salt of coconut oil fattyacid, 35 parts of dodecyl alcohol pentaglycol ether and 30 parts ofcoconut oil fatty acid N,N-bis-(fl-hydroxyethyD-amide, as Well as 100ml. of a galactomannan thickener prepared by pasting 4 g. ofgalactomannan with 20 ml. of ethanol and adding thereto 200 ml. of hotwater, are admixed with the dye paste, the Whole is made up to 1 literwith water and the impregnation liquor thus prepared is brought to atemperature of 30-40". The pH of this liquor is about 3.5-4.

Polyacrylonitrile tow, the fibers of which have a polymerization numberof about 35,000 and possess about 46 millimols of sulfonic acid groupsand 17 millimols of carboxyl groups as dyesites, per 100 g. of fibers,is impregnated with this liquor, the fibers are squeezed off to a liquorcontent of 110%, calculated on the dry weight of the fibers, and steamedfor 20 minutes with saturated steam at 102 under slight excess pressure.

The dyed goods are then rinsed several times with 45 warm water andtreated with an aqueous solution containing 4 g. per liter of anantistatic and 2 g. per liter of a fabric softener.

Excellently level, deep bluish red fibers are obtained.

Even better results are obtained when fixing the dye in the padded fibermaterials in this and the following examples with slightly superheatedsteam of about 103-104", in lieu of saturated steam.

Coconut oil fatty acid N,N-bis-(,B-hydroxyethyl)-amide is produced bycondensing coconut oil fatty acid methyl TABLE 1 Example Dye assistantcomposition Number 2 35 parts of sodium or potassium salt of coconut oilfatty acid; 35 parts of tetradecyl alcohol decaglycol ether; 30 parts oflauric acid N,N-bis-(B-hydroxycthyD-amide.

3- 35 parts of bis-(B-hydroxyethyD-ammonium salt of lauric acid; 35parts of dodecyl alcohol pentaglycol ether; 30 parts of coconut oilfatty acid N ,N-bis-(fl-hydroxyethyl)- amt e.

4 35 parts of ammonium salt of coconut oil fatty acid; 30 parts of thecondensation product of palmitic acid and ethylene oxide in a molarratio of 1:7; 35 parts of lauric acid monoethanol amide.

5 1 part of N-methyl-N,N-bis-(B-hydroxyethyl)ammonium salt of laurie ormyristic acid; 3 parts of addition product of 2 mols of styrene oxideand 50-60 mols of ethylene oxide to 1 mol of stearyl-diethylenctriamine;1 part of laurcilc acid or myristic acid N,N-bis-(;8 hydroxyethyl)- amie.

6 1 part of N-methylN,N-bis-(6,y-dihydroxyoropyl)-am monium salt ofcoconut oil fatty acid; 1 part of stearyldiethylenetriamine polyglycolether having 17 ethyleneoxy groups; 1 part of coconut oil fatty acid N,N-bis- (B hydroxyethyD-amide.

7 1 part of sodium or potassium salt of cocoaut oil fatty acid; 1 partof addition product of 2 mols of styrene oxide and 50-60 mols ofethylene oxide to 1 mol of stearyl-diethylenetriamine; 1 part of lauricor myristic acid N ,N-bis- (fl hydroxyethyl)-amide.

8 35 parts of bis-(B-hydroxyethyD-ammonium salt of lauric acid; 35 partsof stearyl-diethylenetriamine polyglycol ether having 11 ethyleneoxygroups; 30 parts of coconut oil fatty acidN,N-bis-(B-hydroxyethyD-amide.

Example 9 20 g. of the yellow dyestuff used in Example 1 are pasted ing. of 80% acetic acid in the cold and dissolved with 600 ml. of hotWater. 4 g. of galcatomannan as acid resistant thickener are slurriedwith 30 ml. of ethanol and mixed with cold water and this mixture isadded to the above solution while stirring. 30 g. of a mixture of 1 partof coconut oil fatty acid bis-(B-hydroxethyl)-ammonium salt, 1 part ofan addition product of 2 mols of styrene oxide and about 55 mols ofethylene oxide to 1 mol of stearyl-diethylenetriamine and 1 part ofcoconut oil fatty acid N,N-bis-(,B-hydroxethyD-amide are then added, thewhole is brought up to one liter with water and the finishedimpregnating liquor is brought to 30-40. The pH of this liquor is about3 to 4.

Polyacrylonitrile tow, having a polymerization degree of about 35,000and about 154 millimols carboxyl dyesites, per g. of fibers, isimpregnated with its liquor and the material is further treated as givenin Example 1.

Excellently level yellow colored material is obtained.

Similar results are obtained with the same procedure if 10 g. of amixture of 1 part of the salt mentioned above, 2 parts of thestearyl-diethylenetriamine polyglycol ether mentioned above and 1 partof coconut oil fatty acid bis- (B-hydroxyethyD-amide are used.

If, instead of the dystufif given, 33.5 g. of a mixture of dyestuffsconsisting of 27 g. of the dyestulf of the CH3 5H.

CHaO

1 5 3 .5 g. of the dyestuff of the formula and 3.0 g. of the dyestuff ofthe formula are used and otherwise the procedure given in Example 9 isfollowed, then excellently level navy blue colored fibers are obtained.

Example 10 g. of the dyestuff of the formula are slurried in 60 g. of80% acetic acid in the cold and dissolved with 600 ml. of hot water. 4g. of galactomannan are slurried with 2 0 ml. of ethanol and mixed withcold water and this mixture is added to the above solution whilestirring. g. of a mixture of 1 part of N- methyl-N-(B-hydroxyethyl)-ammonium salt of coconut oil fatty acid, 1 part ofstearyl-diethylenetriamine polyglycol ether having 17 ethyleneoxy groupsand 1 part of coconut oil fatty acid N,N-bis-(B-hydroxyethyD-amide arethen added, the whole is made up to one liter with water and thefinished impregnating liquor is heated to 3040". The pH of this liquoris about 3 to 4.

Polyacrylonitrile tow or slubbing of the type used in the precedingexamples is impregnated with this liquor and the material is furthertreated as given in Example 1.

Excellently level red colored material is obtained.

Example 11 10 g. of the yellow dyestuff used in Example 1, 5 g. of thered dyestuff used in Example 1 and -8 g. of the blue dyestuif used inExample 1 are pasted with 30 g. of cold aqueous 85% formic acidsolution, and 200 ml. of hot water are added thereto.

g. of the dye assistant composition used in Example 1 as well as 100 ml.of aqueous 2.5% carob bean flour thickener solution are admixed with thedye paste, the Whole is made up to 1 liter and the impregnation liquoris heated to a temperature of 30-40". The pH of this liqnor is about2.8.

Polyacrylonitrile tow is impregnated with this liquor, the fibers aresqueezed off to a liquor content of 110% and steamed for 20 minutes withsaturated steam at 101 under slight excess pressure.

The dyed goods are then rinsed several times with warm water and treatedwith a solution containing 4 g. per liter of an antistatic and 2 g. perliter of a fabric softener.

Excellently level, deep bluish red fibers are obtained.

Similar results are obtained when using in the above procedure in lieuof formic acid, 40 g. of crystalline tartaric acid mixed with 40 ml. ofwater for making up the dyestuff paste.

The pH of the impregnation liquor ready for use is then 3.2.

By using as the acidifying agent in the above example sulfuric acid inan amount of 4% H 80 per liter of impregnation liquor, whereby the pH ofthe latter is 2.1, similar good results are obtained.

16 Similar results, but, depending on the type of fiber and dyestuff,affording slightly inferior color yields, are obtained if the mixturementioned in Example 1, of fatty acid ammonium salt, polyglycol etherand fatty acid amide is replaced by an equal amount of one of the dyeassistant compositions given below:

TABLE II Example Number 12 1 part of bis-(,d-hydroxyethyl)ammonium saltof coconut oil fatty acid; 1 part of stearyl-diethylcnetriamincpolyglycol other having 17 cthylencoxy groups.

13 1 part of sodium or potassium salt of coconut oil fatty acid, 2 partsof addition product of 2 mols of styrene oxide and -60 mols of ethyleneoxide to 1 mol of stearyl-diethyl enetriamine.

14 1 part of N-methyl-N -(B-hydroxycthy1)ammonium salt of lauric acid; 1part of nonylphcnyl-pentaglycol other.

15 1 part of tris-(B-hydroxyethyl)-ammonium salt of coconut oil fattyacid; 2 parts of stearyl-diethylenetriarnine polyglycol ether having 17ethyleneoxy groups.

16 1 part of bis-(dhydroxycthyl)-ammonium salt of coconut oil fattyacid; 1 part of coconut oil fatty acid-di-(fi-hydroxyethyl)-amidepolyglycol ether having 15-17 ethyleneoxy groups.

17 1 part of dimathyl ammonium salt of coconut oil fatty acid; 1 part ofoctylphcnoxyacetic acid polyglycol ethcr having 3-5 et-hylcncoxy groups.

18 1 part of morpholininm or pyridinium salt of coconut oil fatty acid;1 part of addition product of 2 mols of 1,2- propylene oxide and 50 molsof ethylene oxide to 1 mol of stearyl-diethylenetriamine.

l9 1 part of bis-(B-hydroxyethyl)-ammoniuru salt of lauric acid; 1 partof addition product of 2 mols of styrene oxide and 50-60 mols ofethylene oxide to 1 mol of stearyldiethylenetriamine.

21 1 part of N-methytN-(ti-hydroxyethyl)ammonium salt of coconut oilfatty acid; 1 part of oleylaminc polyglycol ether having 7 ethylencoxygroups.

22 1 part of N-methyl-N-(dhydroxyethyl)ammonium salt of coconut oilfatty acid; 1 part of addition product of 1 mol of styrene oxide and50-60 mols of ethylene oxide to 1 mol of stearyl-diethylenetriamine.

23 1 part of bis-(dhydroxyethyl)ammonium salt of lauric acid; 1 part. ofcoconut oil fatty acid B-arninocthylester polyglycol ether having 8ethyleneoxy groups.

24 1 part of bis-(ti-hydroxycthyl)-ammoniurn salt of pclargonic acid; 1part of stearoyl-dicthylenetriamine polyglycol ether having 17ethylcneoxy groups.

25 1 part of ethyl ammonium salt of coconut oil fatty acid; 1 part ofaddition product of 2 mols of styrene oxide and 50-60 mols of ethyleneoxide to 1 mol of stcaryl-dietliylenetriamine.

26 1 part of sodium or potassium salt of coconut oil fatty acid;

1 part of octylphenol polyglycol ether having 7 ethyloneoxy groups.

27 1 part of his-(fl-hydroxyethyl)-ammonium salt of coconut oil fattyacid; 1 part of dodecyl alcohol pentaglycol ether.

28 1 part of sodium or potassium saltof coconut oil fatty acid;

1 part of decyl alcohol hexaglycol ether.

part of Nanethyl-N-(B-hydroxyethyl) ammonium salt of lauric acid; 1 partof tetradecyl alcohol hexaglycol other.

30 1 part of tris-(dhydroxyethyl)-ammonium salt of coconut oil fattyacid; 1 part of dodecyl alcohol pentaglycol ether.

of N-methyl-N,N-bis-(fl-hydroxycthyl)-ammonium part of dodecyl alcoholpentaglycol 31 2 parts salt of myristic acid; 1 ether.

32 1 part of dimethyl-ammonium salt of coconut oil fatty acid; 1 part ofdodccyl alcohol pentaglycol ether.

33 1 part of morpholine salt of coconut oil fatty acid; 1 part ofdodecyl alcohol pentaglycol ether.

34 1 part of bis-(B-hydroxyethyl)ammonium salt of lauric acid; 1 part ofdodecyl alcohol pentaglycol ether.

35 1 part of bis-(fl-hydroxyethyl)ammonium salt of coconut oil fattyacid; 1 part of dodecyl alcohol decaglycol ether.

36 1 part of N-methyl-N-(B-hydroxyethyl)ammonium salt of coconut oilfatty acid; 1 part of tetradecyl alcohol hcxaglycol ether.

TABLE II-Continued Example Number 37- 1 part ofN-Inethyl-N-(B-hydroxyethyl)ammonium salt of coconut oil fatty acid; 1part of tetradccyl alcohol heptaglycol ether.

38 1 part of bis(oz-methyl-fl-liydroxyethyl)ammonium salt of coconut oilfatty acid; 1 part of dodecyl alcohol pentaglycol ether.

39 1 part of bis(fl-hydroxyethyl)ammonium salt of coconut oil fattyacid; 1 part of coconut oil fatty acid N,N-bis- (IS-hydroxyethyD-amide.

40 1 part of bis-(Bhydroxyethyl)ammonium salt of pelargonic acid; 1 partof coconut oil fatty acid pentaglycol ether.

41 1 part of ethylammonium salt of coconut oil fatty acid;

1 part of coconut oil fatty alcohol pentaglycol ether.

42 1 part of sodium or potassium salt of coconut oil fatty acid;

1 pat of coconut oil fatty acid N ,N -bis-(B-hydroxyethyl)- arm e.

43 2 parts of N-methyl-N,N-bis-(fi-hydroxyethyD-ammonium salt of lauricacid; 1 part oflauric acid N ,N -bis-(B-hydroxyethyl)-amide.

44 1 part of N-methyl-N,NbiS-(l ,'y-dihydroxypropyD-ammonium salt ofcoconut oil fatty acid; 1 part of coconut oil fatty acidN,N-bis-(fl-hydroxyethyl)-amide.

By using, with otherwise the same procedure as given in Example 1,instead of the 40 g. of the dye assistant mentioned in that example, 10,20 or 30 g. of the mixture given in the second column of the followingTable HI as dye assistants, and employing the acid given in the thirdcolumn of said table in the amount stated, dyeings having similarproperties are obtained.

TABLE III Ex. No. Dye assistant composition Acid 46 1 part ofN-methyl-N,N-bisQG-hydroxyethyl)- 50 g. of glaammonium salt of coco-oilfatty acid; 12 parts cial of the condensation product of stearic acidacetic and ethylene oxide in a molar ratio of 1:7. acid. 47- 1 part ofcoconut oil fatty acid diethanol- 50 g. of

amide; 1 part of lauryl alcohol hexaglycol tartaric ether. acid. 48- 1part of octylphenoxy acetic acid N,N-bis-(/3- 50 g. of

hydroxyethyD-amide; 1 part of coconut oil tartaric fatty acidpentaglycol ether. acid.

Example 49 20- g. of the dyestuif of the formula are pasted in 150 g. of80% acetic acid in the cold and dissolved with 600 ml. of hot water. 4g. of galactomannan are pasted with 20 ml. of ethanol and mixed withcold water and this mixture is added to the above solution whilestirring. 30 g. of a mixture of 1 part of coconut oil fatty aciddi-(B-hydroxyethyl)-ammonium salt and 1 part of an addition product of 2mols of styrene oxide and 5060 mols of ethylene oxide to 1 mol ofstearyl-diethylenetriamine are then added and the whole is made up to 1liter with water. The finished impregnating liquor is heated to 3040.The pH of this liquor is about 3-4.

Polyacrylonitrile plush of the same fiber material as the tow dyed inExample 1 is impregnated with this liquor, the material is squeezed outto a liquor content of 100% and the goods are steamed for 20 minuteswith saturated steam at 102 under slight excess pressure.

The dyed goods are then rinsed several times with 45 warm water, thentreated with a solution which contains 4 g. per liter of antistatic and2 g. per liter of fabric softener, and dried.

Excellently level yellow-colored material is obtained.

If the mixture of coconut oil fatty acid di-(B-hydroxyethyl)-ammoniumsalt and an addition product of styrene oxide and ethylene oxide tostearyl-diethylenetriamine given above is used in a Weight ratio of 1:3instead of 1:1 and otherwise the procedure given in the example isfollowed, similar results are obtained.

Similar results are also obtained by using 4050 g. of acetic acid,formic acid or tartaric acid instead of 150' g. of 80% acetic acid, withotherwise the same procedure as given in the example.

Similar results are also obtained by using in lieu of 30 g. of the dyeassistant composition used in Example 49, only 5, 10 or 20 g. thereof.

Example 50 20 g. of the dyestuff of the formula Cur-0112011 Q C-NN N(5H. N+ ta are slurred in 100 g. of 80% acetice acid in the cold anddissolved with 600 ml. of hot Water. 4 g. of galactomannan thickener areslurried with 20 ml. of ethanol and mixed with cold water and thismixture is added to the above solution while stirring. 30 g. of amixture of 3 parts of an addition product of 2 mols of styrene oxide and50-60 mols of ethylene oxide to 1 mol of stearyl-diethylenetriamine and1 part of coconut oil fatty acid di- (li-hydroxyethyl)-ammonium salt arethen added, the Whole is made up to one liter with water and thefinished impregnating liquor is heated to 30-40. The pH of this solutionis about 3-4.

Polyacrylonitrile piece goods are impregnated with this liquor and thegoods are further treated as given in Example 49.

Excellently level blue colored material is obtained.

Example 51 20 g. of the same dyestuff as used in Example 50 are slurriedin 100 ml. of 80% acetic acid in the cold and dissolved with 600 ml. ofhot water. 10 g. of carob bean flour thickener which have been slurriedwith 20 ml. of ethanol and mixed with cold water are added to thissolution while stirring. Then 5 g. of the polyglycol ether obtained bycondensing stearyl diethylenetriamine with per mol thereof, about 17ethyleneoxy groups and 5 g. of coconut oil fatty acidN,N-bis-(fi-hydroxyethyl)amide, are added, the whole is made up to oneliter with water and the temperature of the impregnating liquor isbrought to 3040-. The pH of this liquor is about 34.

Polyacrylonitrile slubbing is impregnated with this liquor and theimpregnated material is treated as described in Example 1.

Excellently level, blue-colored slubbing is obtained.

If, with otherwise the same procedure, instead of the 10 g. of the dyeassistant composition given in Example 51, 10, 20 or 30 g. of theproducts or mixtures given in the following Table IV are used, thendyeings having similar properties are obtained.

oil fatty acid N,N-bis-(B-l1ydroxyethyl)amide.

TABLE 'IV-Conthfiucil Example Number 1 part of octyphenol polyglycolether having 4 ethylene oxide groups; 1 part of coconut oil fatty acidN,N-bis- If, with otherwise the same procedure, instead of, in all, 30.7g. of the dyestuff mixture given in Example 1, the dyestuffs or mixturesof dyestufis given in Column II of the following Table V are used in theamounts given,

(fihydmxyethyn'amlde 5 then dyeings of the shades given in Column HI areob- 56 1 art of coconut oil fatt acid hexagl 'col ether; 1 part ofoconut oil fatty acid l LN-bis-(fi-hgdroxyethyh-amide. tamed whlch alsohave good propertles' TABLE V Ex. No. II III 57 20 grams:

" O Czfis N Blue.

(C2H5)2N N(C2 5)2 0+ 58 20 grams:

i =N B h- Blue. N+ H1 (kHz,

59 20 grams:

- Z Cl I1 Blue. 3H: 3

60 20 grams:

l CH3 00H; 0H=OH-NH -0 OH: Yellowf+ a C 3 61 20 grams:

C=NN=N N02 C Yellow. (311 62 Mixture of 15 grams:

C=N-N=I;I N02 C1 CH and 20 grams I=N --N Q ZnCla Green. I CHzCHzOH 63Mixture of 27 grams:

D :4 1 omomon C a TABLE V-Continued III grams:

Green.

QNUJEBM or 86 10 grams:

Red.

87 Mixture of parts:

20 parts:

Double zinc chloride of- 10 parts:

/ N l a):

5 parts:

CH; N

and 26 parts of dam-i119 Black.

Example 88 A mixture of 10 of the dyestuif of the formula 5 g. of thedyestufi of the formula and 8 g. of the dyestufi of the formula ZnClaPolyacrylonitrile tow consisting of fibers of polyacrylonitrile havingan average molecular weight of about 60,000 to 70,000 and adyestuif-binding equivalent value of about 55 millimol, consistingessentially of sulfonic acid groups, per 100 grams of fibers isimpregnated with this liquor, the fibers are squezed off to a liquorcontent of 100% and steamed for 20 minutes with superheated steam at103. The dyed goods are then rinsed several times with 45 warm water andthen treated with a solution containing 4 g. per liter of an antistaticand 2 g. per liter of a fabric softener and dried.

Fibers dyed an excellently level, deep red-brown shade are obtained.

Example 89 20 g. of the dyestuif of the formula H(J NCHa N -N=N N(C2H5)2211C113 are slurried in 60 ml. of 80% acetic acid in the cold anddissolved with 600 ml. of hot water. g. of carob bean flour thickenerwhich has been slurried with 20 ml. of ethanol and mixed with cold waterare added while stirring to this solution. Then 10 g. of nonylphenolpolyglycol ether containing ethyleneoxy groups are added, the whole ismade up to one liter with water and the impregnating liquor is broughtto 30-40". The pH of this liquor is about 3-4.

'Polyacrylonitrile slubbing of an acrylic fiber material as used in thepreceding example is treated with this are slurried in 150 ml. of 80%acetic acid in the cold and dissolved with 600 ml. of hot water. 4 g. ofgalactomannan thickener which have been slurried with 20 ml. of ethanoland mixed with cold water are added to this solution while stirring.Then 10 g. of an addition product of 2 mol of styrene oxide and about 55mols of ethyleneoxide to stearyl diethylenetriamine are added and theprocedure described in Example 88 is followed using polyacrylonitrileplush instead of tow.

Level, yellow-colored plush is obtained.

If instead of the dyestuff mentioned, the dyestulf of the formula isused and the procedure given above is followed, then level,green-colored plush is obtained.

It, with otherwise the same procedure, instead of the 10 g. of the dyeassistant composition used in Example 90, 10, 15 or 40 g. of theproducts or mixtures given below are used as carrier, then dyeingshaving similar properties are obtained.

T LE liquor following the procedure described in Example 88. AB VI -Aslubbing dyed a very elven red shade is obtained. fi g Dyefissistantcomposition Similar results are obtained on using corresponding amountsof formic or tartaric acid instead of acetic acid. 91 Dodecyl 81001101Pentaglycol ether- 92 Decyl alcohol hexaglycol ether. If instead of thenonylphenol polyglycol ether men- 93 g g l l fi l g fi i t h i I 94 0ecy 3C0 0 603g YCO e er. tioned, octadecanol polyglycol ether having 3to 5 ethyl 95" Tetmdecylalcohol heptaglycolether enemy groups or anOleylamme p y y ether 96 Coconut oil fatty acid pentaglyeol ether. ing 7ethyleneoxy groups is used then with otherwi 97.. 1 part of thecondensation product of coconut oil fatty acid fi-amjno-ethyl ester and,per mol thereof; 10 mols of the same procedure, similar red dyemgs onacrylic fiber ethyilene oxidet; l t r t oi 1 th polyglycol etherrlfbtalned by con ensing s earyie yene riamine wit per mo mammal areobtamed' thereof; 2 mols of styrene oxide and about mols of ethyleneoxide. Example 98 The condensation product of nonylphenoxyacetic acidwith, per mol thereof, 4 mols of ethylene oxide. 20 g. of the dyestuifof the formula S 50 CHQO N If, instead of the dyestuif given in Example89, one of 01 those given in the following table is used and otherwise athe procedure given in the example is followed, then excellently leveldyed goods are also obtained of the H3 55 shades given in column 3 ofthe table.

TABLE VII Shade on No. Dyestufi polyacrylom'trlle fibres j 99 Q 2 I H01Yellow.

CH3 H2N-k NH:

N=N 100 I H01 Do.

(EH30 HzN \N)NH2 TABLE VII-Continued Shade on No. Dyestufipolyacrylonitrile fibres 101 /C=NN=T- N 0 2 01- \1\II CH3 O a 0 CH3'CCH3 102 CCH=CHNH -0 CH; 01-

f+ CH C--N=N-NN 02 C1 Reddish yellow.

104 Same as Example 81 in Table V Yellow;

omnN-omo o N=N=C- 01- Reddish yellow. HaC- -N H 1-C(CH;)2

T Reddish orange. Q

C-N s LII? CH=CHC- 01- Orange, CH3

HsCC-N H (C 2H5) HN- 'NH(C 1H5) HsC- C/ 0 Ha 108 l 01'' Red.

C O O C 2115 0 (CH3): CHzCHaCl 109 C-CH -CH N\ C1" D0.

N CH3 1 110 Same as in Example 65 in Table V Do.

HO---lfiI-CH3 111 G-N=N-N (C2 s) 2 ZnCla Blueish red.

I? C Ha --G (CH3): /CH CH$C1 112 J-CH=CHN 01; Red violet:

1 CH3 C Ha TABLE VIIContinued Shade on No. Dyestufi polyaerylonltrilefibres 113 Same as in Example 78 in Table V Rde Violet 114 Same as inExample 79 in Table V Do.

- (I) C 2H5 01- Greenlsh blue.

115 (C2H5)2N 0/ (C: 5)z

I Cl C H:

1 H a s C H N 2 s): 0/

/ I ZnClr Reddish blue.

C H: 1 1 C CH:O

/" @T Z 01 B n a lue;

120 F g NH:

0 H38 Or Do. H +/C H2-CH2\ 0 I IH-O OH1CHQN\ /CH:

I 011 -0 Hz 121 Same as in Example 64111 Table V Do.

122 Same as in Example 69 in Table V Do.

3 123 -HS 04 Bluelsh green.

0 H3O 124 -N=N N 0 ZnCla' Blue.

TABLE VII-Continued Shade on No. Dyestufi polyaerylonitrile fibresH--CH3 N+ 13s (CHmN-QN: 01- Orange. III CH CH F HCH3 H w N+ I N CH Ierr. 137 IF C1- DO.

I Cl

138 N(CHz) -N -CH CHaOSOa" Blue.

CH3 II I O NH;

021150 out 139. -N=N-N 01- D0.

]l' NHz 14o N=N ZnClf Scarlet.

I g CH3 C2H50- 141 N=N@T ZnClr Blue.

I|I CH (3H2 fi CONH2 Example 142 19.2 g. of the red dyestutf of theformula FNLCE 0.11.

6.2 g. of the yellow dyestuff of the formula and 5.3 g. of the bluedyestulf of the formula s CHaO CZHS 21101 CHgCHzOH III CH3 Kreuzlingen,Switzerland), the whole is made up with water to one liter and the readyimpregnating liquor is heated to a temperature of 30-40". The pH of thisliquor is about 3.5 to 4.

Polyacrylonitrile top, the fibers of which consist of apolyactylonitrile having a polymerization degree of about 35,000 andpossessing per 100 g. thereof about 46 millimols of sulfonic acid groupsand 17 millimols of carboxyl groups, is impregnated with this liquor,the fibers are squeezed oil to a liquor content of 140% and steamed for20 minutes with superheated steamat 103 under slight excess pressure.

The dyed goods are then rinsed several times with 45 warm water andtreated with a solution which contains 4 g. per liter of an antistaticagent and 2 g. per liter of a fabric softener.

Excellently level, deep bluish-red colored top (slubbing) is obtained.

By using, with otherwise the same procedure, instead of 40 g. of thecondensation product given in Example 142, 30 g. of the condensationproduct of 1 equivalent 'fatty acid, consisting of a mixture of lauricacid and myristic acid (molar ratio 1:1), with 2 equivalents oftriethanola-mine, equally deep shades on tows are obtained.

Similar results are also obtained when using in the above example, equalamounts (15 g.) of coconut oil fatty acid diethanolamide and in lieu ofacetic acid, 45 g. of 80%-formic acid per liter, or when using 15 g. oflauric acid mono-ethanolarnide and the same amount (80 ml.) of'60%-acetic acid.

If, with otherwise the same procedure as used in Example 142, instead ofin all 30.7 g. of the dyestuff mixture given in the example, thedyestuffs or dyestuff mixtures given in Column III of the followingTable VI-I-I are used in the amounts given in Column H, then dyeings onpolyacrylonitrile fiber of the shades given in Column W which haveequally good properties, are obtained.

TABLE VIII Ex. No. II III IV 143 20 grams Same as Example 57 Blue. 144..do Same as Example 58. Do.

Same as Example 59-. D0.

Yelllojw 33.5 grams. 150 griamsnn Same as Example 64 B Same as Example78. Same as Example 79- Same as Example 80- Same as Example 81 1) Sameas Example 82- Same as Example 83- Same as Example 84- Yellow Same asExample 85. Green ..do Same as Example 86- Red. do Same as Example 87Black.

Example 174 g. of the yellow dyestuif of the formula and g. of the bluedyestufl used in Example 142 are dissolved in 150 ml. of cold 80%-aceticacid and 200 ml. of hot water are poured in 10 g. of the condensationprodnet of coconut oil fatty acid and 1.5 equivalents of diethanolamine(according to Example 18 of U.S. Patent No. 2,089,212), dissolved in 200ml. of hot water, and 200 ml. of 7.5% galactomannan thickener solutionare added to this solution and the whole is made up to one liter withcold water. The pH of the liquor is about 2.5 to 3.

Polyacrylonitrile top is impregnated with this liquor at a temperatureof 40, the fibers are squeezed out to a liquor content of and thensteamed with saturated steam for 15 minutes at 100-102. The dyed goodsare then rinsed in a Lisseuse machine with warm water containing anantistatic of a cation active fatty acid imidazoline derivative type (4g./liter) and then dried.

Excellently level, voluminous top is obtained which is dyed a deep greencolor.

Example 175 27 g. of the blue dyestuff used in Example 142 are dissolvedin ml. of cold 60% acetic acid and 250 ml. of hot water are added. Asolution of 8 g. of the condensation product from 1 mol of coconut oilfatty acid and 2 mols of triethanolamine (produced according to Example12 of U3. Patent No. 2,089,212) in ml. of hot water and 300 ml. of a hot4% galactomannan thickener solution are added to this solution and themixture is made up to one liter with water. The pH of the liquor isabout 3-3.5. Polyacrylouitrile fabric of acrylic fibers as used inExample 88 is impregnated therewith at a temperature of about 40,squeezed out to a liquor content of about 90% and then the fabric istreated for 25 minutes under slight excess pressure and at a temperatureof about 102, with saturated steam in a steamer. The dyed goods are thenrinsed several times with an aqueous solution containing 4 g. per literof an antistatic of a cation active fatty acid imidazoline derivativetype, and finally, are dried.

Fabric dyed evenly in a full blue shade is obtained.

Example 176 15 g. of the yellow dyestuii used in Example 174, 7.2 g. ofthe blue dyestuff of the formula I oo 2)zN CHa CHaOSOa' C I I o o O NIHand 4.8 g. of the blue dyestuff of the formula are pasted with 60 ml. ofcold 80%-acetic acid, and 200 ml. of hot water are added thereto.

200 ml. of a 2% galactomannan solution in 100 ml. of hot water as wellas 10 g. of a migration-controlling dye assistant consisting of thecondensation product of coconut oil fatty acid and 2 equivalents ofdiethanolamine are added to this solution, the whole is made up to oneliter and the impregnation liquor prepared is brought to a temperatureof 30-40". The pH of this liquor is about 3.5-4.

Polyacrylonitrile tow is impregnated with this liquor, the fibers aresqueezed 01f to a liquor content of 100% and steamed for 20 minutes withsaturated steam at 102 under slight excess pressure.

The dyed goods are then rinsed several times with 45 warm water andtreated with a solution containing 4 g. per liter of an antistatic agentand 2 g. per liter of a fabric softener.

Excellently level, bright yellowish-green fibers are obtained.

1. A PROCESS FOR THE CONTINUOUS DYEING OF ACRYLIC FIBER MATERIALS,COMPRISING (A) IMPREGNATING ACRYLIC FIBER MATERIAL HAVING ACID DYESITESWITH THICKENED AQUEOUS ACID LIQUOR OF BASIC DYESTUFF, AT A TEMPERATUREBELOW THE DRAWING TEMPERATURE OF THE DYESTUFF, WHICH LIQUOR CONTAINS (I)A DYE ASSISTANT COMPOSITION CONSISTING ESSENTIALLY OF: (A) AWATER-SOLUBLE SALT OF A SATURATED ALIPHATIC MONOCARBOXYLIC FATTY ACIDHAVING 8 TO 14 CARBON ATOMS WITH A MONO- TO DIVALENT CATION SELECTEDFROM THE GROUP CONSISTING OF ALKALI METAL ION, AMMONIUM ION, LOWERALKYL-SUBSTITUTED AMMONIUM ION, HYDROXYLOWER ALKYL-SUBSTITUTED AMMONIUMION, AND, FOR EVERY 3 PARTS BY WEIGHT OF (A) IN SAID COMPOSITION ATLEAST ONE PART OF A MEMBER SELECTED FROM THE CLASS CONSISTING OF (B)POLYGLYCOLETHER, ($) AMIDE AND (B/$) POLYGLYCOLETHER-AMIDE MIXTURES,SAID POLYGLYCOLETHER (B) BEING OBTAINED AS (I) CONDENSATION PRODUCT OF AMEMBER SELECTED FROM THE GROUP CONSISTING OF A SATURATED FATTY ALCOHOLOF FROM 8 TO 14 CARBON ATOMS AND A SATURATED FATTY ACID OF FROM 8 TO 14CARBON ATOMS, AND, PER MOL OF SAID MEMBER, 4 TO 12 EQUIVALENTS OFETHYLENE OXIDE, OR AS (II) CONDENSATION PRODUCT FROM THE REACTIONPRODUCT OF A HIGHER FATTY ALCOHOL OF FROM 8 TO 20 CARBON ATOMS AND ANALIPHATIC POLYAMINE HAVING AT LEAST 2 AND NOT MORE THAN 4 BASIC NITROGENGROUPS SEPARATED FROM EACH OTHER BY FROM I TO 3 CARBON ATOMS, IN A MOLARRATIO OF ABOUT 1:1 TO 1:2 AND, PER MOL OF SAID REACTION PRODUCT, FROM 10TO 60 MOL OF ETHYLENE OXIDE, 0 TO 2 MOL OF PROPYLENE OXIDE AND 0 TO 2MOL OF STYRENE OXIDE, SAID AMIDE ($) BEING THAT OF A SATURATED ALIPHATICMONOCARBOXYLIC ACID HAVING FROM 8 TO 14 CARBON ATOMS AMIDIGIED BY AMEMBER SELECTED FROM THE GROUP CONSISTING OF MONO- AND DI-HYDROXY-LOWERALKYL-AMINES AND LOWER ALKYL ETHERS THEREOF, IN A MOLAR RATIO OF(ACID):(AMINE) OF 1:1 TO ABOUT 1:2, WHICH DYE ASSISTANT COMPOSITION ISADDED IN AN AMOUNT OF AT LEAST ABOUT 2 GRAMS PER LITER OF SAIDIMPREGNATION LIQUOR; (II) ACID-MEDIUM-COMPATIBLE THICKENER IN SUFFICIENTAMOUNT TO IMPART TO THE RESULTING IMPREGNATION LIQUOR A VISCOSITY OF ALEAST ABOUT 30 CENTIPOISES; (III) A WATER-SOLUBLE STRONG ACID INSUFFICIENT AMOUNT TO IMPART TO SAID LIQUOR A PH UP TO ABOUT 4, (B)REMOVING EXCESS LIQUOR FROM THE IMPREGNATED ACRYLILC FIBER MATERIAL TOLEAVE ON EVERY 100 PARTS BY WEIGHT OF THE SAID MATERIAL AT LEAST ABOUT80 PARTS BY WEIGHT OF LIQUOR; (C) STEAMING THE RESULTING IMPREGNATEDMATERIAL, AND (D) RINSING THE STEAMED MATERIAL AND DRYING THE SAME.